Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene

© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA..

The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, π-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-π-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal π donation and without significant π/δ backbonding contributions.

Medienart:

E-Artikel

Erscheinungsjahr:

2020

Erschienen:

2020

Enthalten in:

Zur Gesamtaufnahme - volume:59

Enthalten in:

Angewandte Chemie (International ed. in English) - 59(2020), 31 vom: 27. Juli, Seite 13109-13115

Sprache:

Englisch

Beteiligte Personen:

Paprocki, Valerie [VerfasserIn]
Hrobárik, Peter [VerfasserIn]
Harriman, Katie L M [VerfasserIn]
Luff, Martin S [VerfasserIn]
Kupfer, Thomas [VerfasserIn]
Kaupp, Martin [VerfasserIn]
Murugesu, Muralee [VerfasserIn]
Braunschweig, Holger [VerfasserIn]

Links:

Volltext

Themen:

π complexes
Actinides
Bonding
Boron
Heterocycles
Journal Article

Anmerkungen:

Date Revised 12.11.2023

published: Print-Electronic

Citation Status PubMed-not-MEDLINE

doi:

10.1002/anie.202004501

funding:

Förderinstitution / Projekttitel:

PPN (Katalog-ID):

NLM309134501